Defect-Free Prussian Blue Analogue as Zero-Strain Cathode Material for High-Energy-Density Potassium-Ion Batteries

Abstract

Prussian blue analogues (PBAs) have been widely studied as cathodes for potassium-ion batteries (PIBs) due to their three-dimensional framework structure and easily adjustable composition. However, the phase transition behavior and [Fe(CN)₆]^4- anionic defects severely deteriorate electrochemical performances. Herein, we propose a defect-free potassium iron manganese hexacyanoferrate (K_1.47Fe_0.5Mn_0.5[Fe(CN)₆]·1.26H₂O, KFMHCF-1/2) as the cathode material for PIBs. The Fe-Mn binary synergistic and defect-free effects can inhibit the cell volume change and octahedral slip during the K-ion insertion/extraction process, so that the phase transformation behavior (monoclinic ↔ cubic) is effectively inhibited, achieving a zero-strain solid solution mechanism employing Fe and Mn as dual active-sites. Thus, KFMHCF-1/2 contributes the highest initial capacity of 155.3 mAh·g^-1 with an energy density of 599.5 Wh·kg^-1 at 10 mA·g^-1 among the reported PBA cathodes, superior rate capability, and cyclic stability over 450 cycles. The assembled K-ion full battery using K deposited on graphite (K@G) as anode also delivers high reversible specific capacity of 131.1 mAh·g^-1 at 20 mA·g^-1 and ultralong lifespans over 1000 cycles at 50 mA·g^-1 with the lowest capacity decay rate of 0.044% per cycle. This work will promote the rapid application of high-energy-density PIBs.